Formulations of 2-(decylthio)ethanamine

ABSTRACT

The present invention is directed to an antimicrobial composition and a method of using said composition, comprising an antimicrobially effective amount of DTEA and an amount of 1-butanol, cyclohexanol, hexyl alcohol, isobutanol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or a mixture thereof effective to result in the antimicrobial composition having a freezing point of less than 0° C. at atmospheric pressure.

BACKGROUND OF THE INVENTION

The present invention is directed to antimicrobial compositions including 2-(decylthio)ethanamine as the active agent which have lower freezing points than known compositions.

2-(Decylthio)ethanamine (hereinafter referred to as "DTEA") is a compound known to possess antimicrobial properties (see, for example, U.S. Pat. Nos. 3,291,683; 4,816,061; and 4,982,004). Compositions including DTEA are often used in cooling water towers, air washing systems and in other outdoor applications. A typical commercial DTEA composition, comprising 15 weight percent DTEA, 15 weight percent propylene glycol, and the balance water, typically begins to form crystals at 10° C. Prior to its use, a DTEA composition is often stored in unheated areas and can be exposed to temperatures and conditions which can cause the DTEA composition to freeze. Such freezing often causes the DTEA composition to separate into different phases or a precipitate to form.

It would thus be desirable to develop antimicrobial compositions with DTEA as the active agent which have lower freezing points than known compositions. However, any additive to the DTEA composition which would help to lower the freezing point of the composition should not substantially affect the composition's antimicrobial properties. Also, any such additive should help to lower the freezing point of the composition for an extended period of time.

The present invention solves the above-indicated problems by providing antimicrobial compositions including DTEA as the active agent which have lower freezing points than known compositions, which remain stable for long periods of time, and which possess essentially the same antimicrobial efficacy as known compositions.

SUMMARY OF THE INVENTION

The present invention is directed to an antimicrobial composition comprising:

a. an antimicrobially effective amount of 2-(decylthio)ethanamine; and

b. an amount of 1-butanol, cyclohexanol, hexyl alcohol, isobutanol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or a mixture thereof, effective to result in the antimicrobial composition having a freezing point of less than 0° C. at atmospheric pressure.

The present invention is also directed to a method for inhibiting microorganisms in a microbial habitat comprising contacting said microbial habitat with an antimicrobially effective amount of an antimicrobial composition comprising:

a. an antimicrobially effective amount of 2-(decylthio)ethanamine: and

b. an amount of 1-butanol, cyclohexanol, hexyl alcohol, isobutanol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or a mixture thereof, effective to result in the antimicrobial composition having a freezing point of less than 0° C. at atmospheric pressure.

DETAILED DESCRIPTION

In the present specification and claims, the term "2-(decylthio)ethanamine" is meant to refer to the compound of the formula:

    CH.sub.3 --(CH.sub.2).sub.9 --S--(CH.sub.2).sub.2 --NH.sub.2

as well as functional derivatives of this compound such as, for example, salts, and in particular, acid addition salts. Such acid addition salts can typically be conveniently prepared by acidifying the 2-(decylthio)ethanamine with a suitable acid such as a mineral acid or a monofunctional or polyfunctional carboxylic acid to obtain the acid addition salt. Such acid addition salts are generally described, for example, in U.S. Pat. No. 4,816,061, incorporated herein by reference. The hydrochloride salt of 2-(decylthio)ethanamine, 2-(decylthio)ethanamine hydrochloride, is preferred.

As used herein, the term "microorganism" is meant to refer to bacteria, fungus, yeast, viruses, and algae.

As used herein, the term "antimicrobially effective amount" refers to that amount of DTEA, or of a DTEA composition of the present invention, needed to exhibit inhibition of selected microorganisms. Typically, this antimicrobially effective amount varies from providing about 0.01 part per million (ppm) to about 5,000 ppm by weight of DTEA to a microbial habitat being contacted with a DTEA composition. Such antimicrobially effective amounts typically vary depending upon the microorganism desired to be inhibited and the specific conditions of the microbial habitat being contacted with the DTEA composition. A preferred effective amount of the DTEA is from about 0.1 ppm to about 500 ppm, more preferably from about 1 ppm to about 50 ppm by weight, of a microbial habitat.

As used herein, the terms "inhibition", "inhibit", or "inhibiting" refer to the suppression, stasis, kill, or any other interference with the normal life processes of microorganisms that is adverse to such microorganisms, so as to destroy or irreversibly inactivate existing microorganisms and/or prevent or control their future growth and reproduction.

As used herein, the term "microbial habitat", refers to a place or type of site where a microorganism naturally or normally lives or grows. Typically, such a microbial habitat will be an area that comprises a moisture, nutrient, and/or an oxygen source such as, for example, a cooling water tower or an air washing system.

Test formulations of 2-(decylthio)ethanamine (DTEA) are made herein by diluting a DTEA concentrate with water and a candidate additive or additives. Control formulations are made by diluting a DTEA concentrate with water only. Unless otherwise stated, all component percentages herein are by weight basis and on an active basis.

A typical DTEA concentrate composition, such as might be prepared from the MEAH process described below, is listed below:

45 percent--2-(decylthio)ethanamine hydrochloride

45 percent--propylene glycol or tetraethylene glycol

7 percent--water

3 percent--DTEA production impurities, such as 1-decene, cysteamine hydrochloride, and others

As used herein, a DTEA concentrate comprising propylene glycol is referred to as DTEA.PG: whereas, a DTEA concentrate comprising tetraethylene glycol is referred to as DTEA.TEG.

Although a typical DTEA concentrate composition will comprise about 45 weight percent 2-(decylthio)ethanamine, it must be appreciated that a typical DTEA concentrate composition might have a 2-(decylthio)ethanamine concentration ranging from about 40 to about 50 weight percent. As such, a typical diluted DTEA formulation used in a commercial setting might have a 2-(decylthio)ethanamine concentration ranging from about 12 to about 19 weight percent. Preferably, the 2-(decylthio)ethanamine concentration in such diluted DTEA formulations is from about 14 to about 16 weight percent. Such variation in the 2-(decylthio)ethanamine concentration may be due to such factors as process conditions, and imprecise dilution measurements.

Two processes are used to produce the DTEA concentrates used herein. The first process, herein referred to as the MEAH process, reacts mercaptoethylamine hydrochloride and decene in either propylene glycol or tetraethylene glycol. Such a process is generally disclosed, for example, in European Patent Application 320783-A. A DTEA concentrate comprising propylene glycol prepared using the MEAH process is referred to herein as MEAH DTEA.PG. Similarly, a DTEA concentrate comprising tetraethylene glycol prepared using the MEAH process is referred to herein as MEAH DTEA.TEG.

The second process, herein referred to as the ETOX process, reacts ethyloxazoline and decyl mercaptan in propylene glycol. Such a process is generally disclosed, for example, in U.S. Pat. No. 4,816,061. A DTEA concentrate comprising propylene glycol prepared using the ETOX process is referred to herein as ETOX DTEA.PG.

Generally, all DTEA.PG formulations used herein are made using the MEAH process concentrate. A control of ETOX DTEA.PG is used along with a MEAH DTEA.PG control. The DTEA concentrate in tetraethylene glycol (DTEA.TEG) is produced by the MEAH process only.

A DTEA concentrate is typically a solid at room temperature and requires melting before dilution. The concentrate is heated in a water bath to 45° C. for the DTEA.PG and to 80° C. for the DTEA.TEG. The DTEA.TEG typically requires more time to melt.

The formulations tested for freeze-thaw properties had the following general composition:

5-35 percent--2-(decylthio)ethanamine hydrochloride

0-57 percent--propylene glycol or tetraethylene glycol

0.05-67 percent--additive or additives

0-3 percent--DTEA production impurities, such as 1-decene, cysteamine hydrochloride, and others

Balance--Water

Fifty grams of each test formulation is made at room temperature by addition of the appropriate amounts of DTEA concentrate, additive or additives, and water to a 2 ounce (0.06 liter) jar. The test formulation is mixed by gently shaking the jar by hand. The DTEA concentrate needs to remain warm during addition or a precipitate may form which should eventually dissolve with mixing. The order of addition of ingredients does not appear to affect the end product. Some additives tested are not soluble in water but are soluble in the DTEA concentrate. Those additives which were insoluble or reacted negatively with the DTEA by forming a precipitate were incompatible when the samples were made. Some became incompatible after completion of a freeze-thaw cycle.

Use of tap water or deionized water does not appear to affect the end product. Even though a commercial product would typically be made with tap water, deionized water is used to eliminate any variables in the test due to changes in water quality.

Because some test formulations foam upon mixing, the samples are allowed to set for several hours until any foam has dissipated. After such foam dissipation, the sample is split into two 25 g aliquots in 1 ounce (0.03 liter) glass or low-density polyethylene jars.

Commercially used DTEA formulations are often stored in polyethylene lined drums. Initially, polyethylene jars are used in conjunction with glass jars to determine if there is a difference in crystal formation with the two wall surfaces. No difference is observed, so glass jars are used exclusively in the remainder of the experiments because the glass jars give better visibility of the sample.

The interaction of selected test formulations and polyethylene is also studied. Polyethylene samples are cut from soft and rigid polyethylene bottles. The polyethylene samples are measured and weighed prior to being placed in 2 ounce (0.06 liter) jars. Fifty grams of selected formulations of DTEA are then added to each jar. The jars are loosely capped and placed at 45° C for one week. The polyethylene samples are rinsed with deionized water, towel dried and allowed to air dry for 30 minutes. The polyethylene samples are then re-weighed and re-measured. No significant differences are seen in either the measurements or the weights of the polyethylene samples after incubation.

The pH of selected test formulations is measured. The tap water used has a higher pH than the deionized water used. As such, test formulations using tap water have a higher pH than test formulations using deionized water. An increase in DTEA concentration generally results in a slight decrease in formulation pH. The measured pH changes are not considered to be significant in the study of freeze-thaw properties.

In determining freeze-thaw properties, the samples are initially screened at 45° C., 25° C., 4° C. and -12° C. The samples are placed at the appropriate temperature for a minimum of 15 hours. The 45° C. samples are placed in a constant temperature cabinet, the room temperature samples are stored in a cabinet in the lab, the 4° C. samples are stored in an environmental chamber, and the -12° C. samples are stored in a freezer. The samples are visually evaluated for color, absence or presence of crystals or of a uniform slush, amount of crystal formation, and size of crystals. The samples are allowed to thaw at room temperature to determine if the mixture is homogeneous upon thawing. If the sample is not homogeneous upon thawing, it is gently shaken to see if the sample would become homogeneous. The samples at 45° C. and at room temperature do not change in 6 weeks so these test temperatures are discontinued. All samples, except one, freeze solid at - 12° C. Therefore, 4° C. becomes the screening temperature of all samples.

Samples that are clear (no crystal formation) at 4° C. are tested at lower temperatures in a constant-temperature water bath. The temperature is set for two hours at 2° C. and the samples are evaluated as described above. The temperature is then lowered 2°-3° C. for another two hours and the samples are re-evaluated. This cycle is repeated until all the samples form crystals.

Selected controls and formulations which form crystals at 4° C. are also tested in the constant-temperature water bath to determine their freezing points. The temperature is set for 18° C. and lowered by 2° C. every two hours as described above until all samples have formed crystals.

ln an attempt to remove particles that may cause crystal formation, selected control formulations are centrifuged for five minutes at 10,000 revolutions per minute (rpm), then ten minutes at 15,000 rpm. The samples are then decanted into clean 1 ounce (0.03 liter) glass jars and tested for freeze-thaw properties.

A single sample tested through several freeze-thaw cycles may exhibit a different form of freezing each cycle. The two aliquots of a sample could exhibit different freezing characteristics at a given temperature. The most desirable property is that the sample will remain clear during several freeze-thaw cycles.

Lowering the temperature of the tested formulations produces a variety of results. The most common are:

1. Formation of a two-phase system where a fine precipitate fills 1/4 to 1/2 of the sample and

is covered by a clear liquid layer.

2. Formation of various-sized immobile and/or mobile crystals ranging from one crystal to filling 3/4 of the sample covered by a clear liquid layer.

3. Formation of a uniform white slush which varies in viscosity from water-like to very thick.

4. Frozen solid with crystals ranging from fine to large, or a mixture of crystal sizes.

5. The sample remains clear.

Table I shows the freezing point results of different DTEA formulations evaluated that are examples of the present invention. Table 11 shows the freezing point results of different DTEA formulations evaluated that are not examples of the present invention.

                                      TABLE I                                      __________________________________________________________________________     Test Formulations including 2-(Decylthio)ethanamine Hydrochloride              Which are Examples of the Present Invention                                                       Additive                                                                               DTEA        Glycol                                                     Concentration                                                                          Concentration                                                                              Concentration                                                                          Freezing                        Ex.                (Weight (Weight Glycol                                                                             (Weight Point*                          No.                                                                               Additive        Percent)                                                                               Percent)                                                                               Type                                                                               Percent)                                                                               (°C.)                    __________________________________________________________________________      1 1-Butanol       10      15      TEG   17.1  -1 (4)                           2 1-Butanol       15      15      PG  15      -3 (4)                           3 1-Butanol       15      15      TEG   17.1  -3 (4)                           4 1-Butanol       20      15      PG  15      -8 (-6)                          5 1-Butanol       20      15      TEG   17.1  -6 (-3)                          6 1-Butanol       30      15      PG  15      -6 (-4)                          7 1-Butanol       30      15      TEG   17.1  -12 (-10)                        8 1-Butanol       40      15      PG  15      -4 (-2)                          9 1-Butanol       50      15      PG  15      -4 (-2)                         10 Cyclohexanol    20      15      PG  15      -4 (-2)                         11 Cyclohexanol    30      15      PG  15      -4 (-2)                         12 Cyclohexanol    30      15      TEG   17.1  -8 (-5)                         13 Cyclohexanol    40      15      PG  15      -8 (-6)                         14 Cyclohexanol/Octanoic                                                                          10/5    15      PG  10      -6 (-4)                            acid**                                                                      15 Cyclohexanol/Octanoic                                                                          10/5    15      PG  15      -2 (2)                             acid**                                                                      16 Cyclohexanol/Octanoic                                                                          10/5/0.5                                                                               15      PG  15      -4 (-2)                            acid/BARDAC 22**                                                            17 Cyclohexanol/Octanoic                                                                          10/5/1  15      PG  15      -4 (-2)                            acid/BARDAC 22**                                                            18 Cyclohexanol/Octanoic                                                                          10/5/1  15      PG  15      -4 (-2)                            acid/Methanol**                                                             19 Cyclohexanol/Octanoic                                                                          10/5/2  15      PG  15      -4 (-2)                            acid/Methanol**                                                             20 DOWANOL EPh Glycol Ether                                                                       20      15      TEG   8.6   -4 (-2)                         21 DOWANOL EPh Glycol Ether                                                                       20      15      TEG 15      -4 (-2)                         22 DOWANOL EPh Glycol Ether                                                                       30      15      PG  15      -8 (-6)                         23 DOWANOL EPh Glycol Ether                                                                       30      15      TEG   8.6   -8 (-6)                         24 DOWANOL EPh Glycol Ether                                                                       30      15      TEG 15      -6 (-4)                         25 DOWANOL EPh Glycol Ether                                                                       40      15      PG  15      -4 (-2)                         26 DOWANOL EPh Glycol Ether                                                                       40      15      TEG   8.6   -10 (-8)                        27 DOWANOL EPh Glycol Ether                                                                       40      15      TEG 15      -8 (-6)                         28 DOWANOL EPh Glycol                                                                             30/0.05 15      TEG    16.1 -6 (-4)                            Ether/Antifoam FG-10                                                        29 DOWANOL EPh Glycol                                                                             30/0.1  15      TEG 15      -10 (-8)                           Ether/Antifoam FG-10                                                        30 DOWANOL EPh Glycol                                                                             10/5    15      PG  15      -4 (-2)                            Ether/Octanoic Acid**                                                       31 DOWANOL EPh Glycol                                                                             10/5/0.5                                                                               15      PG  15      -4 (-2)                            Ether/Octanoic                                                                 acid/BARDAC 22**                                                            32 DOWANOL EPh Glycol                                                                             10/5/1  15      PG  15      -4 (-2)                            Ether/Octanoic                                                                 acid/BARDAC 22**                                                            33 DOWANOL EPh Glycol                                                                             10/5/1  15      PG  15      -4 (-2)                            Ether/Octanoic                                                                 acid/Methanol**                                                             34 DOWANOL EPh Glycol                                                                             10/5/2  15      PG  15      -4 (-2)                            Ether/Octanoic                                                                 acid/Methanol**                                                             35 DOWANOL PPh Glycol Ether                                                                       20      15      TEG   8.6   -2 (0)                          36 DOWANOL PPh Glycol Ether                                                                       20      15      TEG 15      -2 (0)                          37 DOWANOL PPh Glycol Ether                                                                       20      15      TEG 25      -2 (0)                          38 DOWANOL PPh Glycol Ether                                                                       30      15      PG  15      -2 (0)                          39 DOWANOL PPh Glycol Ether                                                                       30      15      TEG   8.6   -6 (-4)                         40 DOWANOL PPh Glycol Ether                                                                       30      15      TEG 15      -3 (-1)                         41 DOWANOL PPh Glycol Ether                                                                       30      15      TEG 25      -1 (2)                          42 DOWANOL PPh Glycol Ether                                                                       40      15      PG  15      -4 (-2)                         43 DOWANOL PPh Glycol Ether                                                                       40      15      TEG 15      -5 (-3)                         44 DOWANOL PPh Glycol Ether                                                                       40      15      TEG 25      -3 (-1)                         45 DOWANOL PPh Glycol Ether                                                                       20/0.5  15      TEG 15      -3 (-1)                            Ether/Ammonium Xylene                                                          Sulfonate                                                                   46 DOWANOL PPh Glycol                                                                             20/0.5  15      TEG 25      -1 (2)                             Ether/Ammonium Xylene                                                          Sulfonate                                                                   47 DOWANOL PPh Glycol                                                                             20/0.5  15      TEG 15      -5 (-3)                            Ether/Sodium Xylene                                                            Sulfonate                                                                   48 DOWANOL PPh Glycol                                                                             20/0.5  15      TEG 25      -1 (2)                             Ether/Sodium Xylene                                                            Sulfonate                                                                   49 Isobutanol      20      15      PG  15      -6 (-4)                         50 Isobutanol      30      15      PG  15      -8 (-6)                         51 Isobutanol      30      15      TEG   17.1  -10 (-8)                        52 Isobutanol      40      15      PG  15      -8 (-6)                         53 Isobutanol      50      15      PG  15      -6 (-4)                         54 Hexyl alcohol   50      15      PG  15      <-15a                           __________________________________________________________________________

                                      TABLE II                                     __________________________________________________________________________     Test Formulations including 2-(Decylthio)ethanamine Hydrochloride              Which are not Examples of the Present Invention                                                    Additive                                                                               DTEA        Glycol                                                     Concentration                                                                          Concentration                                                                              Concentration                                                                          Freezing                       Ex.                 (Weight (Weight Glycol                                                                             (Weight Point*                         No. Additive        Percent)                                                                               Percent)                                                                               Type                                                                               Percent)                                                                               (°C.)                   __________________________________________________________________________     C-1 Control (ETOX process)                                                                         --      15      PG  15      10 (13)                        C-2 Control (ETOX process)                                                                         --      35      PG  35      11 (13)                        C-3 Control (MEAH process)                                                                         --       5      PG   5      4 (RT)                         C-4 Control (MEAH process)                                                                         --       5      TEG   6.2   4 (RT)                         C-5 Control (MEAH process)                                                                         --      10      PG  10      10 (21)                        C-6 Control (MEAH process)                                                                         --      10      TEG   12.5  4 (RT)                         C-7 Control (MEAH process)                                                                         --      15      PG  15      10 (13)                        C-8 Control (MEAH process)                                                                         --      15      TEG   8.6   4 (RT)                         C-9 Control (MEAH process)                                                                         --      15      TEG 15      14 (16)                        C-10                                                                               Control (MEAH process)                                                                         --      35      PG  35      17 (19)                        C-11                                                                               Control (MEAH process)                                                                         --      35      TEG   20.6  24 (27)                        C-12                                                                               Control (MEAH process)                                                                         --      35      TEG 35      >24                            C-13                                                                               Control (Solid DTEA)                                                                           --      15      --   0       4 (22)                        C-14                                                                               Control (Solid DTEA)                                                                           --      15      PG  15       4 (22)                        C-15                                                                               Control (Solid DTEA)                                                                           --      15      TEG 15       4 (22)                        C-16                                                                               Control (Solid DTEA)                                                                           --      35      PG   5      I                              C-17                                                                               Control (Solid DTEA)                                                                           --      35      TEG  5      I                              C-18                                                                               Simulated ETOX process                                                                         --      35      PG   5      11 (13)                        C-19                                                                               Simulated ETOX process                                                                         --      35      PG  35      I                              C-20                                                                               Simulated ETOX process                                                                         --      35      TEG  5      11 (13)                        C-21                                                                               Simulated ETOX process                                                                         --      35      TEG   20.6  15 (17)                        C-22                                                                               Acetic acid      5      15      PG  15      4 (RT)                         C-23                                                                               Acetic acid     10      15      PG  15      4 (RT)                         C-24                                                                               Acetic acid     15      15      PG  15      4 (RT)                         C-25                                                                               ACTINOL D25LR Tall Oil                                                                           0.1    5      PG   5      4 (RT)                         C-26                                                                               ACTINOL D25LR Tall Oil                                                                           0.1   10      PG  10      4 (RT)                         C-27                                                                               ACTINOL D25LR Tall Oil                                                                            0.25  5      PG   5      I                              C-28                                                                               ACTINOL D25LR Tall Oil                                                                            0.25 10      PG  10      4 (RT)                         C-29                                                                               ACTINOL D25LR Tall Oil                                                                            0.25 15      PG  15      4 (RT)                         C-30                                                                               ACTINOL D25LR Tall Oil                                                                           0.5    5      PG   5      I                              C-31                                                                               ACTINOL D25LR Tall Oil                                                                           0.5   10      PG  10      I                              C-32                                                                               ACTINOL D25LR Tall Oil                                                                           0.5   15      PG  15      4 (RT)                         C-33                                                                               ACTINOL D25LR Tall Oil                                                                          1      15      PG  15      4 (RT)                         C-34                                                                               ACTINOL D25LR Tall Oil                                                                           1.5   15      PG  15      4 (RT)                         C-35                                                                               Ammonium xylene sulfonate                                                                        0.1   15      PG  15      10 (13)                        C-36                                                                               Ammonium xylene sulfonate                                                                         0.25 15      PG  15      10 (13)                        C-37                                                                               Ammonium xylene sulfonate                                                                        0.5    5      PG   5      I                              C-38                                                                               Ammonium xylene sulfonate                                                                        0.5   10      PG  10      10 (21)                        C-39                                                                               Ammonium xylene sulfonate                                                                        0.5   15      PG  15      10 (13)                        C-40                                                                               Ammonium xylene sulfonate                                                                         0.75 15      PG  15      10 (13)                        C-41                                                                               Ammonium xylene sulfonate                                                                       1      15      PG  15      13 (22)                        C-42                                                                               Ammonium xylene sulfonate                                                                         1.25 15      PG  15      I                              C-43                                                                               Ammonium xylene sulfonate                                                                        1.5   15      PG  15      I                              C-44                                                                               Ammonium xylene sulfonate                                                                       2      15      PG  15      I                              C-45                                                                               AMMONYX LO          0.25                                                                               15      PG  15      10 (14)                        C-46                                                                               AMMONYX LO        0.5   15      PG  15      10 (14)                        C-47                                                                               AMMONYX LO       1      15      PG  15      10 (14)                        C-48                                                                               AMMONYX LO       2      15      PG  15      10 (14)                        C-49                                                                               Antifoam FG-10     0.05 15      TEG   16.1  4 (RT)                         C-50                                                                               Antifoam FG-10    0.1   15      TEG 15      4 (RT)                         C-51                                                                               BARDAC 22         0.5   15      PG  15      4 (RT)                         C-52                                                                               BARDAC 22        1      15      PG  15      4 (RT)                         C-53                                                                               1-Butanol       10      15      PG  15      0 (RT)                         C-54                                                                               1-Butanol/Octanoic acid**                                                                      1/1     15      PG  15       4 (23)                        C-55                                                                               1-Butanol/Octanoic acid**                                                                      1/2     15      PG  15      <4 (23).sup.b                  C-56                                                                               1-Butanol/Octanoic acid**                                                                      1/5     15      PG  15      I                              C-57                                                                               1-Butanol/Octanoic acid**                                                                      5/1     15      PG  15       4 (23)                        C-58                                                                               1-Butanol/Octanoic acid**                                                                      5/2     15      PG  15       4 (22)                        C-59                                                                               1-Butanol/Octanoic acid**                                                                      5/5     15      PG  15      <4 (23).sup.b                  C-60                                                                               1-Butanol/Octanoic acid**                                                                      10/1    15      --   0       4 (22)                        C-61                                                                               1-Butanol/Octanoic acid**                                                                      10/1    15      PG   5       4 (22)                        C-62                                                                               1-Butanol/Octanoic acid**                                                                      10/1    15      PG  10       4 (22)                        C-63                                                                               1-Butanol/Octanoic acid**                                                                      10/1    15      PG  15       4 (22)                        C-64                                                                               1-Butanol/Octanoic acid**                                                                      10/2    15      PG  15      0 (2)                          C-65                                                                               1-Butanol/Octanoic acid**                                                                      10/5    15      PG  15      0 (2)                          C-66                                                                               Calcim chloride  2      15      PG  15      4 (RT)                         C-67                                                                               Cyclohexanol/Octanoic                                                                          1/1     15      PG  15       4 (23)                            acid**                                                                     C-68                                                                               Cyclohexanol/Octanoic                                                                          5/1     15      PG  15       4 (23)                            acid**                                                                     C-69                                                                               Cyclohexanol/Octanoic                                                                          5/2     15      PG  15       4 (22)                            acid**                                                                     C-70                                                                               Cyclohexanol/Octanoic                                                                          10/1    15      PG  15      0 (2)                              acid**                                                                     C-71                                                                               Cyclohexanol/Octanoic                                                                          10/2    15      PG  15       4 (22)                            acid**                                                                     C-72                                                                               Cyclohexanol/Octanoic                                                                          10/5    15      --   0      I                                  acid**                                                                     C-73                                                                               Cyclohexanol/Octanoic                                                                          10/5    15      PG   5      I                                  acid**                                                                     C-74                                                                               Decanedioic Acid**                                                                              5      15      --   0      I                              C-75                                                                               Decanedioic Acid**                                                                              5      15      TEG 15      I                              C-76                                                                               Dimethyl acetamide                                                                              5      15      PG  15      4 (RT)                         C-77                                                                               Dimethyl acetamide                                                                             15      15      PG  15      4 (RT)                         C-78                                                                               Dimethyl acetamide                                                                             25      15      PG  15      4 (RT)                         C-79                                                                               Dipropylene glycol                                                                              5      15      PG  15      4 (RT)                         C-80                                                                               Dipropylene glycol                                                                             15      15      PG  15      4 (RT)                         C-81                                                                               Dipropylene glycol                                                                             25      15      PG  15      4 (RT)                         C-82                                                                               DOWANOL DPM Glycol Ether                                                                       10      15      TEG   8.6   4 (RT)                         C-83                                                                               DOWANOL DPM Glycol Ether                                                                       10      15      TEG 15      4 (RT)                         C-84                                                                               DOWANOL DPM Glycol Ether                                                                       10      15      TEG 25      4 (RT)                         C-85                                                                               DOWANOL DPM Glycol Ether                                                                       20      15      TEG   8.6   4 (RT)                         C-86                                                                               DOWANOL DPM Glycol Ether                                                                       20      15      TEG 15      4 (RT)                         C-87                                                                               DOWANOL DPM Glycol Ether                                                                       20      15      TEG 25      4 (RT)                         C-88                                                                               DOWANOL DPM Glycol Ether                                                                       30      15      TEG   8.6   4 (RT)                         C-89                                                                               DOWANOL DPM Glycol Ether                                                                       30      15      TEG 15      4 (RT)                         C-90                                                                               DOWANOL DPM Glycol Ether                                                                       30      15      TEG 25      4 (RT)                         C-91                                                                               DOWANOL EPh Glycol Ether                                                                       10      15      TEG   8.6   0 (2)                          C-92                                                                               DOWANOL EPh Glycol Ether                                                                       10      15      TEG 15      2 (4)                          C-93                                                                               DOWANOL EPh Glycol                                                                             1/1     15      PG  15       4 (23)                            Ether/Octanoic acid**                                                      C-94                                                                               DOWANOL EPh Glycol                                                                             1/2     15      PG  15       4 (23)                            Ether/Octanoic acid**                                                      C-95                                                                               DOWANOL EPh Glycol                                                                             1/5     15      PG  15      I                                  Ether/Octanoic acid**                                                      C-96                                                                               DOWANOL EPh Glycol                                                                             5/1     15      PG  15       4 (23)                            Ether/Octanoic acid**                                                      C-97                                                                               DOWANOL EPh Glycol                                                                             5/2     15      PG  15       4 (23)                            Ether/Octanoic acid**                                                      C-98                                                                               DOWANOL EPh Glycol                                                                             5/5     15      PG  15      I                                  Ether/Octanoic acid**                                                      C-99                                                                               DOWANOL EPh Glycol                                                                             10/1    15      PG  15      2 (4)                              Ether/Octanoic acid**                                                      C-100                                                                              DOWANOL EPh Glycol                                                                             10/2    15      PG  15      4 (22)                             Ether/Octanoic acid**                                                      C-101                                                                              DOWANOL PPh Glycol Ether                                                                       10      15      TEG   8.6   0 (2)                          C-102                                                                              DOWANOL PPh Glycol Ether                                                                       10      15      TEG 15      2 (4)                          C-103                                                                              DOWANOL PPh Glycol Ether                                                                       10      15      TEG 25      4 (RT)                         C-104                                                                              DOWANOL PPh Glycol Ether                                                                       40      15      TEG   8.6   I                              C-105                                                                              DOWANOL PPh Glycol                                                                             1/1     15      PG  15       4 (23)                            Ether/Octanoic Acid**                                                      C-106                                                                              DOWANOL PPh Glycol                                                                             5/1     15      PG  15       4 (23)                            Ether/Octanoic Acid**                                                      C-107                                                                              DOWANOL PPh Glycol                                                                             5/2     15      PG  15       4 (23)                            Ether/Octanoic Acid**                                                      C-108                                                                              DOWANOL PPh Glycol                                                                             10/1    15      PG  15      2 (4)                              Ether/Octanoic Acid**                                                      C-109                                                                              DOWANOL PPh Glycol                                                                             10/2    15      PG  15       4 (22)                            Ether/Octanoic Acid**                                                      C-110                                                                              DOWANOL PPh Glycol                                                                             10/5    15      PG  15      I                                  Ether/Octanoic Acid**                                                      C-111                                                                              DOWFAX 2A1        0.5   15      PG  15      4 (RT)                         C-112                                                                              DOWFAX 2A1         0.75 15      PG  15      10 (RT)                        C-113                                                                              DOWFAX 2A1       1      15      PG  15      4 (RT)                         C-114                                                                              DOWFAX 2A1        1.5   15      PG  15      I                              C-115                                                                              DOWFAX 3B2        0.5   15      PG  15      4 (RT)                         C-116                                                                              DOWFAX 3B2       1      15      PG  15      4 (RT)                         C-117                                                                              DOWFAX XD-8292   1      15      PG  15      4 (RT)                         C-118                                                                              Ethanol         20      15      PG  15      4 (RT)                         C-119                                                                              Ethanol         30      15      PG  15      4 (RT)                         C-120                                                                              Ethanol         40      15      PG  15      4 (RT)                         C-121                                                                              Ethanol         50      15      PG  15      4 (RT)                         C-122                                                                              Ethylene glycol  5      15      PG  15      4 (RT)                         C-123                                                                              Ethylene glycol 15      15      PG  15      4 (RT)                         C-124                                                                              Ethylene glycol 25      15      PG  15      4 (RT)                         C-125                                                                              Ethylene glycol 35      15      PG  15      4 (RT)                         C-126                                                                              GENAMIN 0-050      0.25 15      PG  15      10 (14)                        C-127                                                                              GENAMIN 0-050     0.5   15      PG  15      10 (14)                        C-128                                                                              GENAMIN 0-050    1      15      PG  15      10 (14)                        C-129                                                                              GENAMIN 0-050    2      15      PG  15      10 (14)                        C-130                                                                              GENAMIN 0-200      0.25 15      PG  15      10 (14)                        C-131                                                                              GENAMIN 0-200     0.5   15      PG  15      10 (14)                        C-132                                                                              GENAMIN 0-200    1      15      PG  15      10 (14)                        C-133                                                                              GENAMIN 0-200    2      15      PG  15      10 (14)                        C-134                                                                              GENAMIN T-020      0.25 15      PG  15      10 (14)                        C-135                                                                              GENAMIN T-020     0.5   15      PG  15      10 (14)                        C-136                                                                              GENAMIN T-020    1      15      PG  15      10 (14)                        C-137                                                                              GENAMIN T-020    2      15      PG  15      10 (14)                        C-138                                                                              Glutaric Acid**  5      15      --   0       4 (22)                        C-139                                                                              Glutaric Acid**  5      15      PG  15       4 (22)                        C-140                                                                              Glutaric Acid**  5      15      TEG 15       4 (22)                        C-141                                                                              Glycerin         5      15      PG  15      13.5 (RT)                      C-142                                                                              Glycerin        15      15      PG  15      13.5 (RT)                      C-143                                                                              Glycerin        25      15      PG  15      4 (RT)                         C-144                                                                              2,5-Hexanediol  20      15      PG  15      4 (RT)                         C-145                                                                              2,5-Hexanediol  30      15      PG  15      4 (RT)                         C-146                                                                              2,5-Hexanediol  40      15      PG  15      4 (RT)                         C-147                                                                              2,5-Hexanediol  50      15      PG  15      4 (RT)                         C-148                                                                              Hexyl alcohol   20      15      PG  15      I                              C-149                                                                              Hexyl alcohol   30      15      PG  15      I                              C-150                                                                              Hexyl alcohol   40      15      PG  15      I                              C-152                                                                              Hexyl alcohol   67      15      PG  15      4 (RT)                         C-153                                                                              Hexylene glycol 10      15      PG  15      4 (RT)                         C-154                                                                              Hexylene glycol 20      15      PG  15      4 (RT)                         C-155                                                                              Hexylene glycol 30      15      PG  15      4 (RT)                         C-156                                                                              Hexylene glycol 40      15      PG  15      4 (RT)                         C-157                                                                              Hexylene glycol 50        10.6  PG  11      0 (2)                          C-158                                                                              Isopropanol     10      15      PG  15      4 (RT)                         C-159                                                                              Isopropanol     20      15      PG  15      2 (4)                          C-160                                                                              Isopropanol     30      15      PG  15      2 (4)                          C-161                                                                              Isopropanol     40      15      PG  15      2 (4)                          C-162                                                                              Isopropanol     50      15      PG  15      2 (4)                          C-163                                                                              KELIG 3000D      1      15      PG  15      I                              C-164                                                                              KELIG 3000D      2      15      PG  15      I                              C-165                                                                              Magnesium chloride                                                                              2      15      PG  15      5 (RT)                         C-166                                                                              Magnesium chloride                                                                              4      15      PG  15      5 (RT)                         C-167                                                                              Magnesium chloride                                                                              6      15      PG  15      I                              C-168                                                                              MARASPERSE B-22  1      15      PG  15      I                              C-169                                                                              MARASPERSE B-22  2      15      PG  15      I                              C-170                                                                              MARASPERSE N-22  1      15      PG  15      I                              C-171                                                                              MARASPERSE N-22  2      15      PG  15      I                              C-172                                                                              N-Methylpyrollidone                                                                              0.5   15      PG  15      5 (RT)                         C-173                                                                              N-Methylpyrollidone                                                                             1      15      PG  15      5 (RT)                         C-174                                                                              N-Methylpyrollidone                                                                             2      15      PG  15      5 (RT)                         C-175                                                                              N-Methylpyrollidone                                                                             4      15      PG  15      5 (RT)                         C-176                                                                              NINOL 11-CM      1      15      PG  15      4 (RT)                         C-177                                                                              NINOL 11-CM      2      15      PG  15      4 (RT)                         C-178                                                                              NINOL 11-CM      5      15      PG  15      I                              C-179                                                                              NINOL 11-CM     10      15      PG  15      I                              C-180                                                                              NINOL 11-CM     20      15      PG  15      I                              C-181                                                                              NINOL 11-CM     30      15      PG  15      I                              C-182                                                                              NORLIG A         1      15      PG  15      I                              C-183                                                                              NORLIG A         2      15      PG  15      I                              C-184                                                                              Octanedioic Acid**                                                                              5      15      --   0      I                              C-185                                                                              Octanoic Acid**  1      15      --   0      <4 (23)                        C-186                                                                              Octanoic Acid**  1      15      PG  15       4 (23)                        C-187                                                                              Octanoic Acid**  1      15      TEG 15      <4 (23)                        C-188                                                                              Octanoic Acid**  2      15      --   0      I                              C-189                                                                              Octanoic Acid**  2      15      PG  15      <4 (23)                        C-190                                                                              Octanoic Acid**  2      15      TEG 15      I                              C-191                                                                              Octanoic Acid**  5      15      --   0      I                              C-192                                                                              Octanoic Acid**  5      15      TEG 15      I                              C-193                                                                              PC 825           1      15      PG  15      4 (RT)                         C-194                                                                              PC 825           2      15      PG  15      I                              C-195                                                                              Polyglycol 26-2  1      15      PG  15      4 (RT)                         C-196                                                                              Potassium chloride                                                                              2      15      PG  15      4 (RT)                         C-197                                                                              Propionic Acid**                                                                                5      15      --   0       4 (22)                        C-198                                                                              Propionic Acid**                                                                                5      15      PG  15       4 (22)                        C-199                                                                              Propionic Acid**                                                                                5      15      TEG 15       4 (22)                        C-200                                                                              Propylene glycol                                                                                5       5      PG  10      4 (RT)                         C-201                                                                              Propylene glycol                                                                                5      15      PG  20      4 (RT)                         C-202                                                                              Propylene glycol                                                                               10       5      PG  15      4 (RT)                         C-203                                                                              Propylene glycol                                                                               15      15      PG    30.2  4 (RT)                         C-204                                                                              Propylene glycol                                                                               25      15      PG    40.2  4 (RT)                         C-205                                                                              Propylene glycol                                                                               35      15      PG    50.2  4 (RT)                         C-206                                                                              Sodium bisulfite                                                                                1      15      PG  15      10 (RT)                        C-207                                                                              Sodium bisulfite/ammonium                                                                        1/0.5 15      PG  15      10 (RT)                            xylene sulfonate                                                           C-208                                                                              Sodium bisulfite/sodium                                                                          1/0.5 15      PG  15      10 (RT)                            xylene sulfonate                                                           C-209                                                                              Sodium citrate    0.5   15      PG  15      4 (RT)                         C-210                                                                              Sodium meta bisulfite                                                                           1      15      PG  15      10 (RT)                        C-211                                                                              Sodium sulfate   2      15      PG  15      I                              C-212                                                                              Sodium sulfite   2      15      PG  15      I                              C-213                                                                              Sodium thiosulfate                                                                              1      15      PG  15      I                              C-214                                                                              Sodium xylene sulfonate                                                                          0.1   15      PG  15      10 (13)                        C-215                                                                              Sodium xylene sulfonate                                                                           0.25 15      PG  15      10 (13)                        C-216                                                                              Sodium xylene sulfonate                                                                          0.5   15      PG  15      10 (13)                        C-217                                                                              Sodium xylene sulfonate                                                                           0.75 15      PG  15      10 (13)                        C-218                                                                              Sodium xylene sulfonate                                                                         1      15      PG  15      13 (22)                        C-219                                                                              Sodium xylene sulfonate                                                                           1.25 15      PG  15      13 (22)                        C-220                                                                              Sodium xylene sulfonate                                                                          1.5   15      PG  15      I                              C-221                                                                              Sodium xylene sulfonate                                                                         2      15      PG  15      I                              C-222                                                                              Sodium xylene   0.5/0.5 15      PG  15      I                                  sulfonate/DOWFAX 2A1                                                       C-223                                                                              Tetraethylene glycol                                                                            5      15      PG  15      5 (RT)                         C-224                                                                              Tetraethylene glycol                                                                            5      35      TEG 40      >24 (50)                       C-225                                                                              Tetraethylene glycol                                                                             6.4   15      TEG 15      4 (RT)                         C-226                                                                              Tetraethylene glycol                                                                           10       5      TEG   16.7  4 (RT)                         C-227                                                                              Tetraethylene glycol                                                                           10      15      PG  15      5 (RT)                         C-228                                                                              Tetraethylene glycol                                                                           10      15      TEG 25      4 (RT)                         C-229                                                                              Tetraethylene glycol                                                                           10      15      TEG   27.1  4 (RT)                         C-230                                                                              Tetraethylene glycol                                                                           15      10      TEG   23.6  4 (RT)                         C-231                                                                              Tetraethylene glycol                                                                           15      15      PG  15      5 (RT)                         C-232                                                                              Tetraethylene glycol                                                                             16.4  15      TEG 25      4 (RT)                         C-233                                                                              Tetraethylene glycol                                                                           20      15      PG  15      5 (RT)                         C-234                                                                              Tetraethylene glycol                                                                           20      15      TEG   37.1  4 (RT)                         C-235                                                                              Tetraethylene glycol                                                                           20      35      TEG   55.2  >24                            C-236                                                                              Tetraethylene glycol                                                                           30      15      TEG   47.1  4 (RT)                         C-237                                                                              Tetraethylene glycol                                                                           40      15      TEG   57.1  I                              C-238                                                                              TRITON X-100      0.5   15      PG  15      4 (RT)                         C-239                                                                              TRITON X-100     1      15      PG  15      4 (RT)                         C-240                                                                              TWEEN 80          0.5   15      PG  15      4 (RT)                         __________________________________________________________________________      Explanation of terms used in Tables I and II:                                  PG  Propylene glycol                                                           TEG  Tetraethylene glycol                                                      RT  Room Temperature                                                           I  Incompatible. The sample was nonhomogeneous either when made or after       freezethaw cycle.                                                              .sup.a A thin liquid layer was observed on the bottom of this sample           .sup.b formed a cloudy liquid at 4° C.                                  *The first number is the temperature where crystals were first observed i      at least one aliquot of the sample. The temperature in parentheses is the      last temperature tested where the sample was clear.                            **Solid DTEA used                                                        

    ______________________________________                                         CHEMICAL FORMULATIONS OF TRADE NAME                                            PRODUCTS USED IN DTEA FREEZE-THAW STUDIES                                      ______________________________________                                         ACTINOL ™ D25LR Tall Oil - High rosin distilled tall oil                    cut with tall oil fatty acid. High rosin content is 25 percent.                (ACTINOL ™ is a trademark of the Arizona                                    Chemical Company; ACTINOL ™ D25LR Tall Oil is a                             product of The Arizona Chemical Company)                                       AMMONYX ™ LO -       29-31   percent                                        Lauryl dimethylamine oxide                                                     Water                           balance                                        (AMMONYX ™ is a trademark of                                                The Onyx Chemical Company;                                                     AMMONYX ™ LO is a product of                                                The Onyx Chemical Company)                                                     Antifoam FG-10 - Polydimethyl siloxane                                                                 10      percent                                        remainder emulsifiers, preservatives and water                                 (Antifoam FG-10 is a product of                                                Dow Corning Corporation)                                                       BARDAC ™ 22 - decyl dimethyl                                                                        50      percent                                        ammonium chloride                                                              Isopropanol             20      percent                                        Water                   30      percent                                        (BARDAC ™ is a trademark of Lonza, Inc.;                                    BARDAC ™ 22 is a product of Lonaz, Inc.)                                    DOWANOL ™ DPM Glycol Ether-                                                 Dipropylene glycol monomethyl ether                                                                    99      percent                                        (DOWANOL ™ is a trademark of                                                The Dow Chemical Company;                                                      DOWANOL ™ DPM Glycol Ether is                                               a product of The Dow Chemical Company)                                         DOWANOL ™  EPh Glycol Ether -                                               Ethylene glycol phenyl ether                                                                           90      percent                                        Diethylene glycol phenyl ether                                                                         10      percent                                        (DOWANOL ™ is a trademark of                                                The Dow Chemical Company;                                                      DOWANOL ™ EPh Glycol Ether is                                               a product of The Dow Chemical Company)                                         DOWANOL ™ PPh Glycol Ether-                                                 Propylene glycol phenyl ether                                                                          93      percent                                        Dipropylene glycol phenyl ether                                                                        7       percent                                        (DOWANOL ™ is a trademark of                                                The Dow Chemical Company;                                                      DOWANOL ™ PPh Glycol Ether is a                                             product of The Dow Chemical Company)                                           DOWFAX ™ 2A1 - Dodecyl(sulfo-                                               phenoxy)benzenesulfonic                                                        acid, disodium salt and                                                        Oxybis(dodecylbenzenesulfonic acid),                                           disodium salt           47      percent                                        Sodium sulfate          1       percent                                        Sodium chloride         3       percent                                        Water                           balance                                        (DOWFAX ™ is a trademark of                                                 The Dow Chemical Company;                                                      DOWFAX ™ 2A1 is a product of                                                The Dow Chemical Company)                                                      DOWFAX ™ 3B2 - Decyl(sulfo-                                                 phenoxy)benzenesulfonic                                                        acid, disodium salt, and                                                       Oxybis(decylbenzenesulfonic acid),                                             disodium salt           47      percent                                        sodium sulfate          3       percent                                        sodium chloride         3       percent                                        Methylene chloride      2       percent                                        Water                           balance                                        (DOWFAX ™ is a trademark of                                                 The Dow Chemical Company;                                                      DOWFAX ™ 3B2 is a product of                                                The Dow Chemical Company)                                                      DOWFAX ™ XD-8292 -                                                          Hexyl(sulfophenoxy)benzene                                                     sulfonic acid disodium salt and                                                Oxybis(hexylbenzenesulfonic acid                                               disodium salt           45      percent                                        Sodium sulfate          3       percent                                        Sodium chloride         3       percent                                        Methylene chloride      2       percent                                        Water                           balance                                        (DOWFAX ™ is a trademark of                                                 The Dow Chemcial Company;                                                      DOWFAX ™ XD-8292 is a product of                                            The Dow Chemical Company)                                                      GENAMIN ™ O-050 - Oleylamine +                                                                      100     percent                                        5 ethylene oxides                                                              (GENAMIN ™ is a trademark of                                                The American Hoechst Corporation;                                              GENAMIN ™ O-050 is a product of                                             The American Hoechst Corporation)                                              GENAMIN ™ O-200 - Oleylamine +                                                                      100     percent                                        20 ethylene oxides                                                             (GENAMIN ™ is a trademark of                                                The American Hoechst Corporation;                                              GENAMIN ™ O-200 is a product of                                             The American Hoechst Corporation)                                              GENAMIN ™ T-200 - Tallowamine +                                                                     100     percent                                        2 ethylene oxides                                                              (GENAMIN ™ is a trademark of                                                The American Hoechst Corporation;                                              GENAMIN ™ T-020 is a product of                                             The American Hoechst Corporation)                                              KELIG ™ 3000D - Lignosulfonate                                                                      100     percent                                        (KELIG ™ is a trademark of                                                  Reed Lignin Incorporated;                                                      KELIG ™ 3000D is a product of                                               Reed Lignin Incorporated)                                                      MARASPERSE ™ B-22 - Sodium                                                                          100     percent                                        lignosulfonate                                                                 (MARASPERSE ™ is a trademark of                                             Reed Lignin Incorporated;                                                      MARASPERSE ™ B-22 is a product of                                           Reed Lignin Incorporated)                                                      MARASPERSE ™ N-22 - Highly                                                                          100     percent                                        purified sodium lignosulfonate                                                 (MARASPERSE ™ is a trademark of                                             Reed Lignin Incorporated;                                                      MARASPERSE ™ N-22 is a product of                                           Reed Lignin Incorporated)                                                      NINOL ™ 11-CM - Coconut diethanolamide                                                              100     percent                                        (NINOL ™ is a trademark of                                                  The Stepan Company;                                                            NINOL ™ 11-CM is a product of                                               The Stepan Company)                                                            NORLIG ™ A - Calcium Lignosulfonate                                                                 100     percent                                        (NORLIG ™ is a trademark of                                                 Reed Lignin Incorporated;                                                      NORLIG ™ A is a product of                                                  Reed Lignin Incorporated)                                                      PC 825 - Lignosulfonic acid,                                                                           100     percent                                        ethoxylated, sodium salt                                                       (PC 825 is a product of                                                        Westvaco Corporation)                                                          TRITON ™ X-100 - Octylphenoxy                                                                       100     percent                                        polyethoxyethanol                                                              (TRITON ™ is a trademark of                                                 The Rohm & Haas Company;                                                       TRITON ™ X-100 is a product of                                              The Rohm & Haas Company)                                                       TWEEN ™ 80 - Polyoxyethylene-20-                                                                    100     percent                                        sorbitan monooleate                                                            (TWEEN ™ is a trademark of                                                  Atlas Chemical Industries, Incorporated;                                       TWEEN ™ 80 is a product of                                                  Atlas Chemical Industries, Incorporated)                                       ______________________________________                                    

Generally, alcohol additives, such as 1-butanol, cyclohexanol, hexyl alcohol, and isobutanol, and glycol ethers, such as ethylene glycol phenyl ether and propylene glycol phenyl ether, give the best reduction of freezing point for a DTEA formulation and are preferred additives. Such additives, or a mixture of two or more such additives, must be used in an amount effective to result in an antimicrobial composition that has a freezing point of less than 0° C. at atmospheric pressure. The use of these alcohol and glycol ether additives also has the added advantage in that they decrease the amount of foam produced during formulation. What foam is produced typically dissipates in a few minutes.

Based on the total weight of 1-butanol, cyclohexanol, hexyl alcohol, isobutanol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or a mixture thereof and 2-(decylthio)ethanamine present in an antimicrobial composition of the present invention, preferably the antimicrobial composition comprises from about 15 to about 95 weight percent 2-(decylthio)-ethanamine and from about 5 to about 85 weight percent 1-butanol, cyclohexanol, hexyl alcohol, isobutanol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or a mixture thereof.

Based upon the total weight of an antimicrobial composition of the present invention, preferrably the antimicrobial composition comprises:

a. from about 12 to about 19 weight percent 2-(decylthio)ethanamine:

b. from about 8 to about 18 weight percent propylene glycol, tetraethylene glycol or a mixture thereof;

c. from about 1 to about 60 weight percent 1-butanol, cyclohexanol, hexyl alcohol, isobutanol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or a mixture thereof: and

d. from about 10 to about 75 weight percent water.

More preferred ranges for the preferred and glycol additives are from about 15 to about 35 weight percent 1-butanol, from about 5 to about 45 weight percent cyclohexanol, from about 45 to about 60 weight percent hexyl alcohol, from about 15 to about 50 weight percent isobutanol, from about 25 to about 45 weight percent ethylene glycol phenyl ether, or from about 15 to about 45 weight percent propylene glycol phenyl ether. Preferably, the antimicrobial composition has a freezing point of less than -4° C. at atmospheric

Another preferred additive, particularly when used with cyclohexanol or ethylene glycol phenyl ether, is octanoic acid when used in a range from about 1 to about 10 weight percent of a total DTEA composition.

Fifty percent hexyl alcohol does not freeze at the lowest temperature tested (-15° C. ). However, a thin liquid layer is observed at the bottom of the sample which indicates some separation of the composition.

Generally, an increase in DTEA concentration causes an increase in the freezing point.

Flash Point Determination of Selected Formulations

From Table I, 1-butanol, cyclohexanol, and isobutanol are seen to be among the best additives in reducing the freezing point for a DTEA formulation. Since the flash points of these alcohols are quite low, the flash point of a DTEA formulation to which these alcohols are added becomes an important consideration in choosing a final formulation. The most desirable formulation should have a flash point above 200° F. (93° C. ) so that it would not be as heavily regulated as formulations below this temperature. If a flash point above 200° F. (93° C. ) is not feasible, it is desirable for the flash point to be above 100° F. (37° C. ) so that the formulation will be classified as a combustible liquid rather than a flammable liquid. The handling regulations for a combustible liquid are generally much more lenient than for a flammable liquid. Several potential candidate formulations were analyzed for flash point. The results are listed in Table III. As can be seen from Table III, many of the compositions of the present invention have acceptable flash points.

                  TABLE III                                                        ______________________________________                                         Flash Points of Selected 15 Percent Formulations of                            2-(Decylthio)Ethanamine Hydrochloride                                                      Additive                                                                       Concentration                                                      Additive    (Weight Percent)                                                                            Flash Point                                           ______________________________________                                         Cyclohexanol                                                                               20           178° F. (81° C.)                        1-Butanol.sup.b                                                                            10           122° F. (50° C.)                        1-Butanol.sup.a                                                                            15           118° F. (48° C.)                        1-Butanol.sup.b                                                                            15           117° F. (47° C.)                        1-Butanol.sup.a                                                                            20           115° F. (46° C.)                        1-Butanol.sup.b                                                                            20           114° F. (46° C.)                        1-Butanol.sup.a                                                                            30           114° F. (46° C.)                        Isobutanol.sup.a                                                                           20           103° F. (39° C.)                        ______________________________________                                          .sup.a 2(Decylthio)ethanamine hydrochloride in propylene glycol                .sup.b 2(Decylthio)ethanamine hydrochloride in tetraethylene glycol       

What is claimed is:
 1. An antimicrobial composition comprising:a. an antimicrobially effective amount of 2-(decylthio)ethanamine; and b. an amount of 1-butanol, cyclohexanol hexyl alcohol, isobutanol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or a mixture thereof, effective to result in the antimicrobial composition having a freezing point of less than 0° C. at atmospheric pressure.
 2. The antimicrobial composition of claim 1 comprising:a. from about 15 to about 95 weight percent 2-(decylthio)ethanamine: andb. from about 5 to about 85 weight percent 1-butanol, cyclohexanol, hexyl alcohol, isobutanol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or a mixture thereof:based on the total weight of 1-butanol, cyclohexanol, hexyl alcohol, isobutanol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or a mixture thereof, and 1-(decylthio)ethanamine.
 3. The antimicrobial composition of claim 1 wherein the 2-(decylthio)ethanamine is in the form of the [2-(decylthio)ethanamine] hydrochloride acid addition salt.
 4. The antimicrobial composition of claim 1 comprising, based upon the total weight of such composition:a. from about 12 to about 19 weight percent 2-(decylthio)ethanamine: b. from about 8 to about 18 weight percent propylene glycol, tetraethylene glycol or a mixture thereof: c. from about 1 to about 60 weight percent 1-butanol, cyclohexanol, hexyl alcohol, isobutanol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or a mixture thereof; and d. from about 10 to about 75 weight percent water.
 5. The antimicrobial composition of claim 4 comprising from about 15 to about 35 weight percent 1-butanol and wherein the antimicrobial composition has a freezing point of less than -4° C. at atmospheric pressure.
 6. The antimicrobial composition of claim 4 comprising from about 5 to about 45 weight percent cyclohexanol and wherein the antimicrobial composition has a freezing point of less than -4° C. at atmospheric pressure.
 7. The antimicrobial composition of claim 4 comprising from about 15 to about 50 weight percent isobutanol and wherein the antimicrobial composition has a freezing point of less than -4° C. at atmospheric pressure.
 8. The antimicrobial composition of claim 4 comprising from about 25 to about 45 weight percent ethylene glycol phenyl ether and wherein the antimicrobial composition has a freezing point of less than -4° C. at atmospheric pressure.
 9. The antimicrobial composition of claim 4 comprising from about 15 to about 45 weight percent propylene glycol phenyl ether and wherein the antimicrobial composition has a freezing point of less than -4° C. at atmospheric pressure.
 10. The antimicrobial composition of claim 4 further comprising from about 1 to about 10 weight percent octanoic acid.
 11. A method for inhibiting microorganisms in a microbial habitat comprising contacting said microbial habitat with an antimicrobially effective amount of an antimicrobial composition comprising:a. an antimicrobially effective amount of 2-(decylthio)ethanamine; and b. an amount of 1-butanol, cyclohexanol, hexyl alcohol, isobutanol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or a mixture thereof, effective to result in the antimicrobial composition having a freezing point of less than 0° C. at atmospheric pressure.
 12. The method of claim 11 wherein the antimicrobial composition comprises:a. from about 15 to about 95 weight percent 2-(decylthio)ethanamine; and b. from about 5 to about 85 weight percent 1-butanol, cyclohexanol, hexyl alcohol, isobutanol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or a mixture thereof:based on the total weight of 1-butanol, cyclohexanol, hexyl alcohol, isobutanol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or a mixture thereof and 2-(decylthio)ethanamine.
 13. The method of claim 11 wherein the antimicrobial composition is used in an amount to provide from about 0.01 part per million to about 5,000 parts per million by weight of 2-(decylthio)ethanamine to the microbial habitat.
 14. The method of claim 11 wherein the 2-(decylthio)ethanamine is in the form of the hydrochloride acid addition salt.
 15. The method of claim 14 wherein the antimicrobial composition further comprises from about 1 to about 10 weight percent octanoic acid.
 16. The method of claim 11 wherein the antimicrobial composition comprises, based upon the total weight of such composition:a. from about 12 to about 19 weight percent 2-(decylthio)ethanamine; b. from about 8 to about 18 weight percent propylene glycol, tetraethylene glycol or a mixture thereof: c. from about 1 to about 60 weight percent 1-butanol, cyclohexanol, hexyl alcohol, isobutanol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or a mixture thereof: and d. from about 10 to about 75 weight percent water.
 17. The method of claim 16 wherein the antimicrobial composition comprises from about 15 to about 35 weight percent 1-butanol and wherein the antimicrobial composition has a freezing point of less than -4° C. at atmospheric pressure.
 18. The method of claim 16 wherein the antimicrobial composition comprises from about 5 to about 45 weight percent cyclohexanol and wherein the antimicrobial composition has a freezing point of less than -4° C. at atmospheric pressure.
 19. The method of claim 16 wherein the antimicrobial composition comprises from about 15 to about 50 weight percent isobutanol and wherein the antimicrobial composition has a freezing point of less than -4° C. at atmospheric pressure.
 20. The method of claim 16 wherein the antimicrobial composition comprises from about 25 to about 45 weight percent ethylene glycol phenyl ether and wherein the antimicrobial composition has a freezing point of less than -4° C. at atmospheric pressure.
 21. The method of claim 16 wherein the antimicrobial composition comprises from about 15 to about 45 weight percent propylene glycol phenyl ether and wherein the antimicrobial composition has a freezing point of less than -4° C. at atmospheric pressure. 